Catalytic hydrogenation of organic compounds



Patented June 15, 1943 CATALYTIC IHYDROGEINATION OF ORGANIC COMPOUNDS OttoSchmidt, lleidelberg Gel-many, assignor, by mesne assignmenta'to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware I No Drawing. Originalapplication April 1, 1931,

anhydrides can bereduced in the gaseous phase system as for example from co mpounds, espewith the aid or hydrogen and of metallic hydrocially of oxygen-containing compounds, such-as genation catalysts at atmospheric pressure. In hydroxides, oxides, carbonates, phosphates, silimost cases, however, as for example in the reduc-, 'cates, nitrates, or also cyanides complex comtion of acetic ethyl ester heterogeneous products pounds as for example iron-cyanides and the have been obtained which contained some aldelike, of the alkali or the alkaline earth or rare hyde and oleflnes. Even the reduction of anhyearth metals, such as potassium, sodium, calcium, drides in the liquid phase with noble metal hyrium or ma n sium, l n h thorium. drogenation catalysts, such as palladium, and at ium d o i f h boron and uslightly elevated pressure up to 4 atmospheres larly m ompounds of the metals giving acids iurnished heterogeneous products consisting With y n, S h a hromiumrmo y u mainly of aldehydes. tungsten, uranium, manganese, vanadium or I have found that in organic compounds havtitanium or mixtures thereof as well as salts oi ing at least 2 carbon atoms and containing the metal acids or several of these compounds. carboxylic acid radicle (i. e. at least 2- oxygen. Th m tal f rmin acids with oxy n m be l atoms conne ted t one carbon t Said employed in the form of the alkali metal, alkaline pounds being, for example, monoor poly-carearth metal or rare earth metal salts of the said boxylic acids containing at least 2 carbon t acids or in the form or their. salts with the hysuch as aliphatic open chain or cycloaliphatic, drogenetin! metals. .8 0 e p pp and aromatic carboxylic acids, and their derivacobalt- Silver zine Vm mfllybdates.

tlves containing at least 2 oxygen atoms conso sanic saltauranatestuns a andthe like nected to one carbon atom, especially of those and in this as the said hydro enati m a s acids which contain at least 8 carbon atoms in s t b p s nt as such. Th solid metals their molecule, the free or latent carboxylic of the 2nd to 4th group 01 t p m. groups can be reduced to alcoholic groups by for e p e Zi e, u ti and aluminum treating the said compounds in th liquid t t may also be employed in the free state for actiat an elevated temperature with hydrogen in the Vating P p s. e Said c eap dv easily av i presence of hydrogenation catalyst at a pressure. able metals being er T Order of of at least 30 atmospheres until the saponiflcas the s id sin le co p is not tion value of the initial materials is considerably l v as a a y ta ed. e a iv t diminished. In order to obtain good results it 40 substances m be i e with o p of the is usually necessary to work under energetic conhydr s tins m t whereupon the Whole ditions at increased temperatures, such as above 111888 is Subjected to a treatmeht wi h hy r 120 c. whereby reducible compoundsof the hydrogenat- An eiiicie'nt activation of the catalysts can be 8 metals are converted Wh ly 01 a least P iobtained by a very fine disintegration of th tially into the free metals. I Otherwise the comcatalytic substances, for example by employing P0 li mi e 1 e p in a melt the catalytic substances alone in a very finely fusible activating substances, suchas alkali metal divided form, or by depositing the catalytic subundl. j w the h drosenstlnc m s stances on large surface carriers, such as fibrous. w r ded. In cases wh n asbestos. powered graphite, silica gel or inert 5o impound! ar to be hydrogenated which still metal powders a the like and/or by adding to contain catalyst poisons, suchas animal fats con the catalytic substances one or more activating taming albuminous matter, catalysts immune substances. Suitable catalytic substances are for i from poisoning, asfior example those containing l example the base-metals, copper, nickel, iron, molybdenum or its compoundsalone or inadmix- Serial No. 527,060.

Divided and this applicatlon July 29, 1941, Serial No. 404,521. 1 In Gelmany November 20, 1925 16 Claims.

consisting of or containing preponderating quan-- titles of the said products.

It is already known that esters of fatty acids of low molecular weight and the corresponding cobalt or silver or mixtures thereof and they may be prepared from their salts, oxides or other compounds, if desired prior to or after an incorporation with activating substances. Compounds of metals which are converted intothe metals during the operation may be'also employed, as

for example salts of cobalt with any organic carboxylic acids. The activating substances may be chosen from compounds of the solid metallic elements of the 1st to 7th groups of the periodic ture with other substances may be employed.

By suitably selecting the catalyst as well as the reaction temperature and the pressures, the reduction can be carried either to a well defined stage, i. e. to the formation of products which contain alcoholic groups or even to products in which the original carboxyl groups are reduced to hydrocarbon radicles. Thus, for example, soya bean oil can be reduced to a mixture of pure alcohols corresponding to thefatty acids of the original oil. In many cases catalysts consisting of nickel provide more energetic reduction than catalysts prepared from cobalt or copper, which latter are particularly valuable for the production of alcohols, whereas the employment of a highly active nickel catalyst may lead to a reductlon to the hydrocarbon stage, especially at higher temperatures, say between 300 and 400 C. The emciency of the catalyst employed, however, depends to a large extent on whether a carrier or other additions are employed. Thus; for example, a catalyst consisting of nickel and activated with chromium provides amost energetic reduction when working in the liquid phase and often leads to the formation of hydrocarbons whereas nickel deposited on,'say, nine times its weight of kieselsuhr. furnishes products with a high saponiflcation value. Catalysts prepared from cobalt with additions of a basic nature, such as alumina, magnesia or potassium hydroxide are particularly suitable for the production of alcohols.

The temperatures employed depend, generally speaking, on the nature of the material under treatment and its volatility; temperatures between 120 and 400 C. are usually employed. For the reduction of the carboxyl groups into alcoholic groups temperatures between about 150 and 300 C. are advantageously employed, whereas the application of temperatures substanflail? above 250 C. favours the formation of by drocarbons especially when working with active catalysts or nickel as mentioned above; if catalysts oi? copper be employed the temperatures may be somewhat higher. The optimum reaction temperature for the production of a certain reaction product depends on the nature of the initial material and on the nature of the catalyst employed.

The pressure employed depends on the nature of the initial materials; any pressure of at least 30 atmospheres, preferably from 100 to 300 atmospheres, or still higher pressures, such as up to 400 or 500 atmospheres, will be applied; straight chain hydrory-carboxylic, carbcxylic acids with 1 branched chains and anhydrldes require usually lower pressures than straight chain saturated acids and their esters. For the reduction of olive oil into the alcohols corresponding to the fatty acids 01' olive oil for example a pressure above- 150 atmospheres is usually necessary whereas hydrosy-octodecanol can be obtained irorn'castor oil at lower pressures as for example at 45 atmospheres. The application of higher pressures usua sshortens the pemd of time required for the reaction. Time, for emple, stearic'methyl ester can be reduced to octodecanol at a pressure of 300 atmospheres in about half the time required when working at a pressure or 200 atmospheres under otherwise equal conditions of working. The period or time required for carrying out the processalsodependsonthemannerinwhichthehydrogen is introduced, and on the homogeneous dispersion of the catalyst within the initial material, intimately stirring and/or spraying the mixture of initial material and catalyst into the re-' action vessel providing for example most satisfying results. The process may be carried out continuously or intermittently in any usual and convenient manner.

The quantity of hydrogen employed is advantageously chosen considerably above that theoretically required for the reduction. In the place of pure hydrogen gaseous mixtures containing the same may also be employed the hydrogen being diluted for example with vapor of water, alcohol, or with nitrogen or carbon dioxide. If desired, diluents inert to the initial materials, such as small quantities of water, or cyclohexane, benzines, phenols, alcohols of high molecular weight may be added, unsaturated compounds being hydrogenated in many cases during the reaction. By the addition of alcohols the reaction is often facilitated on working with free acids, esters formed thereby being apparently more easily reduced than freeacids.

In this manner even carboxylic acids, and their derivatives of the aforesaid nature, having a very oleic acid or train oil acid, other acids of vegetal origin, that is of vegetable and animal oils or fats, or oxidation products of paraflln wax or glycerides, such as soya bean oil, coconut oil, castor oil, tallow train oils, and the anhydrides, or mixtures thereof with salts of the corresponding acids, and benzoic alkyl esters and esters of homologues of benzoic esters, naphthenic esters and the like can be converted into alcohols oi the aliphatic series, having a high molecular weight which hitherto have not been available commercially. When employing acids and the like which contain double linkages or other readily reduciblegroups, as for example nitrogroups, a hydrogenation oi the double linkages, a reduction of the nitro groups andthe like often takes place first during the hydrogenation. If hydroxycarbox'ylic acids, or their derivatives, such as many cases, the original secondary hydroxyl group being apparently less resistant to reduction. The alcohols obtained may find useful application in the production, for example, of artificial waxes or cosmetic preparations or of washlng, emulsifying or wetting agents by sulphonation, for which Purposes they may be employed even in acid baths or together with hard water, The alcohols may also find useful application for softening natural or synthetic rubber or rubberlike substances, such as gutta percha and the alcohols having a long chain may be esterifled with long chain carboxylic acids, such as montanic acid, for the formation of synthetic waxes. The

high molecular alcohols obtained may be esterified with low molecular carboxylic acids, such as acetic acid, and the esters may find useful application as assistant solvents in the lacquer or varnish industries or as swelling or gelatinizing agents. Wax-like esters having. very valuable properties are often formed in the reaction according to the present invention. and these are formed from high molecular alcohols formed and from remainders of the non-reduced acids, or their derivatives. some portion'of the acids, or their derivatives, being reduced to alcohols which latter then react with the acid not yet reduced with the formation of esters, the saponiilcation value being thus reduced by from it to 3 3; on the other hand the saponiilcation value may be reduced to from it to zero if alcohol; in the free and esterifled state are mainly desired, a reduction by ab either these wax-like'products solely are obtained A or mixtures thereof with a certain predetermined content of alcohols or of hydrogenated glycerides. This can be obtained by reducing the pressure and/or temperature depending on the nature of the initial material and on the activity of the catalyst employed. These wax-like products may be employed as substitutes for bees-wax, spermacetti and the like or may be converted into alcohols by further treatment according to the present invention. The wax-like esters obtained may be employed in the place of or in conjunction with dressing or impregnating agents in the textile industries or as assistants in the preparation of polishes.

The following examples will further illustrate how the said invention may be carried out in practice, but the invention is not restricted to these examples.

' Example 1 A mixture. of carboxylic acids consisting of lower members of the fatty acid series and obtained by the destructive oxidation of a low melting point paraffin wax withthe aid of nitrogen dioxide is incorporated with per cent its weight of pyrophorous cobalt powder (obtainable by reducing cobalt carbonate (Merck) in the pulverulent state at about 350C. with'hydrogen) and then treated at 200, C. with hydrogen at a pressure of 200 atmospheres until the decrease of pressure has ceased. The catalyst is then filtered oil and the filtrate'is subjected to distillation at about 12 millimeters (mercury gauge) whereby a mixture of alcohols having a hydroxyl value of 290 is obtained at atemperature between 80 and 200 C. The distillation residue which is obtained in a quantity of about per cent of the whole material subjected to distillation contains waxlike bodies. employed as such for further operations.

Example 2 A commercial mixture of the anhydrides of palmitic and stearic acids is incorporated with 3 per cent its weight of a catalyst consisting of metallic cobalt and potassium oxide which has Examp e 3 A catalyst of metallic cobalt which has been treated with hydrogen for 36 hours .at 360 C. and which has been activated by the addition of 2 per cent of vanadic acid is added to stearicacid and the latter is treated with hydrogen at 225 C. under a pressure of 200 atmospheres until no more hydrogen is absorbed. The distillation of the reaction product in vacuo after careful removal of the catalyst yields mainly octodecyl pressure is kept at 200 atmospheres until hydrowax, namely the octodecyl ester of stearic'acid,

which remains behind after the distillation in' some cases may be subjected toreduction again so that the yield of alcohol is practically complete.

A similar procedure is followed in the reduction of other carboxylic acids, such as butyric acid, succinic acid, colophony, linoleic acid,

montanic acid, naphthenic acids, acids from the oxidation of paraflin and like waxes, or'mixtures with salts of carboxylic acids,. as for example the ammonium salt of stearic acid and the like.

Example 4 A mixture of cobalt and copper carbonates is precipitated from an aqueous solution of 70 parts of cobalt nitrate and 30 parts of copper nitrate by adding potassium bicarbonate. After carefully washing the paste is stirred with 1 part of potassium bichromate, dried, pulverized and treated withhydrogen-for 18 hours at 300 C. Stearic methyl esterto which about 3' per cent of this catalyst has been added is treated with hydrogen at 230 C. in a rotary autoclave and the gen is no longer absorbed. The contents of the autoclave are subjected to a distillation during which mainly octodecyl alcohol. (melting point 56 C.) passes over between 200 and 210 C. at 11 millimeters mercury gauge in a yield of about 95 per cent. The wax formed during the reduction and left behind after the distillation may be subjected to reduction again so that the yield of alcohol is almost complete. The alcohol may find useful application as a softening agent in the rubber industry.

Instead of the aforesaid catalyst, a catalyst from commercial cobalt carbonate may be employed without the addition of bichromate and The catalysts separated off can be alcohol having a boiling point of from 203 to' the reaction may be carried out at 250 C. and at 300 atmospheres. If, in this case, the reaction be stopped after one hour, the product possesses a saponification value of 108, is solid, pale yellow and consists of about '70 per cent of octodecyl stearate and 15 per cent each of octodecyl alcohol and initial material together with traces of hydrocarbons. This mixture may find useful ,application in the production of. sizes for the textile industries.

If desired, equal parts of phenol and of stearic methyl ester may be mixed with 5 per cent by weight of the catalyst described in Example 1 and heated in a rotary autoclave to 220 C. while forcing in hydrogen at a pressure of 200 atmospheres until the absorption of hydrogen has ceased. By fractional distillation of the product hexahydrophenol and octodecyl alcohol are obtained in a yield each of more than per cent. Instead of phenol, benzene or like hydrogenizable compounds, hydrogenated benzene or other inert compoundsmay be employed.

' Example 5 Cobalt carbonate and aluminum oxide are made into a paste with water ground in a ball mill' and'kept for 36 hours in 'a current of hydrogen at 350 C., the initial compounds'be'ing employed in such quantities that, after the reduction, the mixture contains 17 per cent of metallic cobalt. 1 metric ton of commercial soya bean oil to which about 7 per cent of this catalyst has been added is treated with hydrogen at 230 C. in a stirring autoclave of about 1.5'cubic meters and the pressure is keptat 200 atmospheres until there is no further absorption of hydrogen, the partial pressure of hydrogen being preferably maintained by intermediately" blowing off the mixture of hydrogen and hydrocarbons formed from glycerol, such as methane and propane, and reintroducing fresh hydrogen. The contents of the autoclave are subjected to a distillation during which in additionto a, small amount of first runnings mainly octodecyl alcohol having a boiling point of from 203 to 210 C. at 11 millimeters mercury gauge and a melting point of about 56 C. passes over. glycerine is mainly converted into propyl alcohols, l.2-propylene glycol and partly into propane and methane. The small amount of wax formed during the reduction and remaining behind after the distillation may be subjected to reduction again so that the yield of alcohol is practically quantitative. In a similar manner waxes, such as bees-wax or carnauba wax may be reduced with the formation of alcohols from the acids in admixture with the alcohols originally contained in the waxes. Under the aforesaid conditions of working coconut fat furnishes a mixture of alcohol containing from 8 to 18 carbon atoms.

By increasing the temperature to 275 C. the octodecyl alcohol is reduced to octodecane which can thus be obtained in a pure form.

By reducing the pressure to about 150 atmospheres a wax-like substance is obtained.

Example 6 Finely powdered kieselguhr is incorporated with per cent or its weight of nickel by treatment with nickel nitrate and reduction and then the whole is stirred with an aqueous solution of about 3 per cent by weight of the nickel or potassium bichromate. After drying and grinding, the mass is treated with hydrogen for 36 hours at 350 C. Soya bean oil is then mixed" with 10 per cent 01 its weight of the catalytic mass and hydrogen is introduced at 200 atmospheres at 200 C. until a sample shows a saponiflcation value or from 150 to 170 and an acid value of from to 20. The product obtained having a melting point of about 60 C..is separated from the catalytic mass which latter may be directly 45 employed for another operation. The wax-like product shows conchoidai fracture surfaces and 1 possesses a high gloss. The process can also be easily conducted in such a manner that any desired ratio of ester and hydrogenated soya bean oil or of ester and octodecanol may be obtained in the products. Generally speaking, products having a high saponiflcation value possess a high hardness and a high gloss, whereas productswith lower saponiflcation values. 1. e. mixture of the ester and alcohols obtained during the reaction are softer and more mat than the storesaid products and possess a lower melting point. Similar products can be obtained from train oil, rapeseed oil and other slycerides. Products having a saponiilcation value 01' about 5% that of the initial material usually possess a crystalline nature like spermaceti. The products obtained may find useful applicationin the textile industries for example as dressing or impregnating agents as such or in conjunction with the hue agents employed for this purpose.

Example 7 cobalt and aluminum nitrates by precipitation and subsequent treatment with hydrogen at from 320 to 850 C., and 2 per cent or the cobalt, 75

By working in this manner the Example 8 Castor oil is heated at 220 C. in a stirring autoclave with 3 per cent of its weight of a cat,-

alyst consisting of cobalt activated by potassium 15 hydroidde and prepared by making cobalt carbonate into an aqueous paste with 1 per cent of its weight of potassium nitrite, drying and treating the mass with hydrogen at 310 C., while introducing hydrogen until a pressure of 45 atmospheres is attained. After 24 hours the reaction product is drawn of! and distilled in *vacuo and furnishes at 18 millimeters oi mercury a distillate passing Over between 217 and 240 C. in a quantity or 50 per cent by weight of 25 the castor oil.

. By increasing the pressure under otherwise qual conditions of working the yield 01 whole distillate can be increased to more than 95 per cent 01' the theoretical yield; the portion of the 0 distillate boiling at from 230 to 240 C., at 18 millimeters of mercury, is practically pure hydroxy-octodecyl alcohol, having smelting point of 65 C. and a liydroxyl value of 382.

Example 9 Adipic di-ethyl ester is incorporated with 3 per-cent of its weight of cobalt which has been prepared by reducing finely powdered cobalt carbonate with hydrogen at 300 C., whereupon the mixture is treated at 190 C. ;with hydrogen at a pressure of 180 atmospheres until the consumption of hydrogen has ceased. After cooling, the oily reaction product is filtered of! from the cobalt and distilled in vacuo. At from150 to 151 C. and 17 millimeters or mercury 1.6-dihydroxyhexane having a melting point of 42 C. is obtained in a yield oi. more than 50. per cent by weight of the initial material. Hexyl alcohol is obtained in the fractions boiling below 150 C.

' Example 10 Montan wax bleached according to the speciflcation of U. 8 Patent No. 1,777,766 and having an acid value of about 140 is esterifled with methyl alcohol by boiling it under reflux for 4 hours with 8/5 oi. its weight of methyl alcohol and 4 of its weight of hydrochloric acid. 100 parts or the methyl ester thus prepared having a saponiflcation value 0! 182 are incorporated with 2 parts of a nickel-kieselguhr catalyst consisting of 1 part of nickel deposited on 5 parts of kieselguhr and heated with hydrogen at about 180 to 200 C. under a pressure oi 100 atmospheres while pressing in hydrogen. As soon as the reaction product has a saponiflcation value of about the hydrogenation is interrupted. A iter iilteringofl! the catalyst, a pale hard wax [187111158 a melting point or C. is obtained on coo g.

Example 11 1000 parts of a product, consisting mainly of montanic acid and obtained byv bleaching deresiniiled montan wax with chromic acid and having a saponiflcation value of 173 and an acid value oi 148, are heated in an autoclave to 220 'by filtration in a heated filter press. solidifies to a colorless waxy mass having a melt- C. together with a catalyst consisting of 58.8 parts of nickel and 1.2 parts of chromium, while pressing in hydrogen up to a pressure of 200 I atmospheres. As soon as the saponiflcation value has been diminished to 88 and the acid value to 14 the reaction productis drawn. oil? and saponified with alcoholic caustic potash. The acids and-unsaponifiable matter are then precipitated with dilute aqueous sulphuric acid whereby a mixture is obtained which possesses an acid value of 83 and can be esterified by boiling for 2 hours at about 120 C. with the aid of 0.04 per cent of concentrated sulphuric acid. The resulting prod- I uct possesses an acid value of 5.6 and is a hard wax-like mass of white shade.

Example 12 gen consumed being replenished and the reaction being stopped as soon as the consumption of hydrogen has ceased. The reaction product is then freed from the catalyst by filtration and subjected to distillation in vacuo. '70 per cent of the product consists of dodecanol boiling at about 142 C. at 11 millimeters of mercury, a small I fraction boiling at 220 C. at 2 millimeters of mercury.

Example 13 10 parts of a catalyst prepared by mixing 30 parts of kieselguhr with a solution of 300 parts of catalyst prepared by making into a paste 100 parts of cobalt carbonate and 0.8 part of potassium nitrite, drying, pulverizing and treating with hydrogen at 325C and the mixture is heated to 240 C. while introducing hydrogen at a pressure of 300 atmospheres until the saponiiication value has decreased to about 60. A prod uct having a melting point of about 55 C. and the shade of a pale bees wax is obtained; it is softer than a product prepared from the same initial material but in the production of which the re-' action is stopped at a higher saponification value of say 130 and which may be employed for polishing purposes for example for wood or 'linoleum. Similar waxy products can be obtained from palm oil.

Example 15 Coconut oil having asaponification value of 245 is mixed with 1.5 per cent its weight of metallic cobalt prepared by treating basic cobalt carbonate containing about 0.5 per cent by weight nickel nitrate in 700 parts of water, precipitating with aqueous sodium bicarbonate, filtering, washing, adding a solution of 3 parts of chromic acid,

drying, pulverizing and treating with hydrogen at about 270 C. are introduced into 90 parts of fused stearic acid directly after the reduction of the catalyst. The mixture of stearic acid and the catalyst is heated in a stirring autoclave at 240 C. while introducing hydrogen until a pressure of 170 atmospheres is attained, heating being continued until a sample shows the saponification value of about 100 of o'ctodecyl stearic ester.

The product is then separated from the catalyst The filtrate is below 100 mixtures of the aforesaid waxy stearic ester and octodecyl alcohol together with a small quantity of acid can be obtained. In this manner the ratio between the different products of sodium carbonate with hydrogen-at about 350 C. and the mixture is heated to 200 C. while forcing in hydrogen at a pressure of 250 atmospheres until the saponification value has decreased to about 100. The semi-solid product consists of esters of the alcohols, formed by the reduction of the acids, and the acids of the oil together withthe alcohols in the free state, the reduction products of glycerine and traces of initial oil. If the product be drawn off from the reaction vessel in the hot state the reduction products of glycerine are evaporated together with water and alcohols of low molecular weight formed from the lower acids of the 011. Products having a saponification value of from '70 to 100 or less pos sess, when employed in small quantities the agreeable odour of lower alcohols, such as octyl or dodecyl alcohols and may be usefully employed as perfumes or fixatives for other perfumes in the of high molecular weight which comprises reacting an ester of a carboxylic acid having more than 8 carbon atoms in the acid radical with hydrogen at a temperature of from 300 to 400 C. and under a pressure of from 100 to 200 atmospheres in the presence of a hydrogenatlng catalyst.

3. The process for the production of alcohols I of high molecular weight which comprises recan be largely varied. In a similar manner mixtures of waxy esters and/or of alcohols can be prepared from mixtures of fatty acids'with different numbers of carbon atoms. In this manner it is possible to prepare waxy products having different properties, for example as regards hardness, gloss and possibility of emulsification according to the desired purpose of application of the said products.

Example 14 Olive oil is mixed with 1.5 per cent of a cobalt acting an ester of a carboxylic acid having more than 8 carbon atoms in the acid radical in the liquid phase with hydrogen at a temperature of from 300. to 400 C. and under a pressure of from to 200 atmospheres in the presence of a hydrogenating catalyst.

4. The process as defined in claim 1 wherein the pressure is at least 30 atmospheres.

5. The process as defined in claim 1 wherein the carboxylic acid is a fatty acid of vegetal origin wherein the reaction is effected in theliquid phase and wherein the hydrogenating catalyst is a base metal hydrogenation catalyst.

thecatalyst is a dimculty reducible hydrogenating metal oxide.

13. The process as defined in claim 1 wherein the ester is a loweraliphatic alkyl ester oi! steeric acid.

14. The process as defined in claim 1 wherein the ester is a lower aliphatic alkyl ester of stearic acid and wherein the catalyst is an activated copper containing hydrogenating catalyst.

15. The process as defined in claim 1 wherein the ester is cocoannt oil.

16. The process as'defined in claim 1 wherein the ester is the methyl ester of stearic acid.

. v 1 OTTO SCHMIDT. 

